Heterocyclic vat dyestuffs



United States Patent HETEROCYCLIC VAT DYESTUFFS Wilhelm Schmidt-Nickels, Little York, N. J., and Lewis J. Lugg, Pen Argyl, 2a., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 28, 1954,

Serial No. 478,171

12 Claims. (Cl. 260-295) This invention relates to the production of novel heterocyclic vat dyestuflfs having the formula 2,772,274 Patented Nov. 27, 1956 7 stituted by chlorine or bromine atoms. ,In the reactants,

RF may be. nitro and R may be alkyl, such, as, methyl, ethyl, propyl, isopropyl, or butyl. Products wherein R is amino are obtained by reduction of the corresponding product in which R is nitro, while products wherein R and/or R are halo are obtained by subsequent halogenationwith chlorine or bromine. The reaction takes place readily in proportions of about one molecular equivalent of the 2,3-dihalo-1,4-naphthoquinone and one molecular equivalent of the pyridine for each acetoacetamide group in the N-aromatic acetoacetamide. Thus, where the N-aromatic acetoacetamide contains one acetoacetamide group, as shown in the reaction portrayed above, the reaction takes place between 1 mole of each of the reactants. Where the N-aromatic acetoacetamide contains two acetoacetamide groups, as in examples 3 and acceptor.

range oi shades of good fastness to Washing, chlorine and light when dyed and printed in the usual manner.

,The dyestuffs of this invention may be produced by the reaction of a 2,3-dihalo-1,4-naphth'oquinone with a pyridine unsubstituted in the 2-position and an Naromatic acetoacetamide of the formula The exact mechanism of the reaction is not clearly understood, but it is believed that it proceeds in the manner portrayed in the following equations wherein 2,3-dichloro- 1,4-naphthoquinone is ,reacted witlr pyridine and-2- acetoacetamino-fluorenone:

It will be understood that in carrying out the foregoing reaction, the reactants may contain inert substituents which do not interfere with the desired reaction. Thus, the aryl residue of the N-aromatic acetoacetamide may comprise a radical of the" benzene ornaplithalene series which may further contain nuclear substituents, fused 4 below, the reaction takes place between 2 moles of the 2,3-dihalo-1,4-naphthoquinone, 2 moles of the pyridine, and 1 mole of the N-aromatic acetoacetamide.

Since the reaction involves liberation of HCl, it is desirable to conduct the reaction in the presence of an acid It is preferable to employ the pyridine reactant in an amount in excess of that required for the instant reaction. The excess pyridine serves as an acid acceptor and as a convenient liquid medium in which to carry out the reaction. However, other liquid media may be employed which boil within or above the range of temperatures required for the reaction wh ich may be frcm about 30 to C. Selection of aliquid medium which boils at the desired reaction temperature facilitates tern perature control since the reaction may then be carried out under reflux. The reaction product is usually insoluble in the liquid medium employed for the reaction and the precipitate may be readily separated by filtration, washing, and the like. However, in instances where the reaction product is soluble in the liquid medium, it may be conveniently separated by drowning in water followed byfiltration, washing, and the like.

suitable sodium or desired salt.

The dyestuffs of thisinvention may be employed for coloring, dyeing or printing film or fibrous material in any form and having a basis of natural or artificial polymeric material, such as cotton or other natural cellulosic potassium compound to produce the 2,772,274 3 4 material, regenerated cellulose, such as derived by the Example 3 viscose or cuprammonium process, or by saponification of cellulose esters, or other material capable of being colored by vat dyestuffs in soluble, dispersed, or pigment A charge of 45 parts by volume pyridine, 4.1 parts by weight bis-acetoacet-benzidine-sulfone of the structure form. 5

The following examples are illustrative of preferred OQ embodiments of this invention and are not to be regarded as limitative. Parts are in grams by weight, in cc. by volume.

Example 1 and 4.5 parts by weight 2,3-dichloro-1,4-naphthoquinone was stirred at reflux for 4 hours. The reaction product A Oharge of 40 Parts by Volume py' Parts y was worked up as described in Example 1. The dyestufi weight Z-acetoacetamino-fluorenone and 3.2 parts by h h apparent structure;

I -oo,NHQ-ONH-oo-ci 2.

Weight 2,3-di0h101'0-1,4-naphtlloqllinofle was Stirred at and gives reddish brown dyeings of good fastness to flux for 4 The Teactloll Product Was filtered Off chlorine and light. The shade turns somewhat yellower at room temperature, washed with pyridine, acetone, on hi water, and dried. The dyestuff has the apparent struc- Example 4 ture:

A charge of 45 parts by volume pyridine, 3.8 parts by weight Naphthol AS-G of the structure o H N OHa-CO-CH OO-NHQQNH-OO-OH,-OO-CH;

l CH1 CH3 \O 0 and 4.5 parts by weight 2,3-dichloro-l,4-naphthoquinone was stirred at reflux for 4 hours. The reaction mixture 0 was poured into 450 parts by volume water. After CWHHOlNI stirring for 30 minutes the reaction product was filtered Found: N=5.76%. .Theory for C30H1604N2Z N= off, washed with warm water until free of pyridine, and 5.98%. dried. The dyestufi has the apparent structure:

I -oo-N -Q-Q1vn-co-ii O I H: CH:

The product dyes cotton from an alkaline hydrosulfite The product dyes orange tints of good iastness propervat in violet shades of good tastness to washing, chloties but is tinctorially not as strong as the {product of rine, and light. 56 Example 3.

Example 2 7 Example 5 A charge of parts by volume pyridine, 4.5 parts A charge of 50 parts by volume pyridine, 3.5 parts by by weight acetoacebbeta-naphthylamide, and 4.5 parts by weight acetoacetanilide, and 4.5 parts by weight 2,3- weight 2,3-dichloro-1,4-naphthoquinone was stirred at redichloro-1,4-naphthoquinone was stirred at reflux for 4 flux tor 4 hours. The reaction product was worked up 60 hours. The reaction product was Worked up as described as described in Example 1. The dyestufi has .the apin Example 1. The dyestufi has the apparent structure:

parent structure:

. o I 7 I (I) mam-Q --OO-NH V a 'm r r a OIIHHOINI I i Found: N=7.42%. Theory for CzaHuOaNaz. N= and gives violet dyeings of a similar shade and the same 7.65%.

fastness properties as the product of Example 1, al- The product dyes pink although tinctorially not very though tinctorially not as strong. a 76 strong, 1

This invention has been disclosed with respect to cer- 4. A process for producing a dyestulf as defined in tain preferred embodiments, and various modifications claim 3 comprising reacting by heating 2,3-dichloroand variations thereof will become obvious to the person 1,4-naphthoquinone, pyridine, and Z-acetoacetaminoskilled in the art. It is to be understood that such modifiuorenone.

fications and variations are to be included within the 5 5. A dyestuif of the formula spirit and purview of this application and the scope of the appended claims.

We claim: 0 1. A dyestuff having the formula I 0 R! -OO--NH N I o 6. A process for producing a dyestufl as defined in OONH AY claim 5 comprising reacting by heating 2,3-dichloro-1,4- naphthoquinone, pyridine, and acetoacet-beta-naphthyl- O amide. wherein Ar represents an aryl radical; R is selected 7. A dyestufi of the formula 8. A process for producing a dyestuif as defined in from the group consisting of hydrogen, nitro, amino and claim 7 comprising reacting by heating 2,3-dichloro-1,4- halo; R is selected from the group consisting of lower naphthoquinone, pyridine, and bis-acetoacet-benzidinealkyl and halo; and n has a value of 0 to 3. sulfone.

2. A process for producing a dyestulf as defined in 9. A dyestuff of the formula 0 O I N N I claim 1 comprising reacting by heating a 2,3-dihalo-1,4- naphthoquinone having the formula 10. A process for producing a dyestuff as defined in claim 9 comprising reacting by heating 2,3-dich1oro-1,4- naphthoquinone, pyridine, and a compound having the Halo formula 0 onaoo-onaoomn ma oo on oo om wherein R is selected from the group consisting of 1137- drogen, nitro, amino and halo, a pyridine having the formula 11. A dyestufli of the formula a. in which the 2-position is unsubstituted, R is selected 0 from the group consisting of lower alkyl and halo, and N n has a value of 0 to 3, and an N-aromatic acetoacetamide of the formula CHs--C0-CHz-CO-NH-Ar wherein l Ar represents an aryl radical.

3. A dyestutf of the formula 12. A process for producing a dyestufl-T as defined In I claim 11 comprising reacting by heating 2,3-dich1oro-L4- 00 \0 0 naphthoquinone, pyridine, and acetoacetanilide. II 0 fl No references cited. 

1. A DYESTUFF HAVING THE FORMULA 